Polyhalogenated bicyclic thiourethanes



lOo liiial United? Quin-n1 Patented Nov. 24, 1964 3,158,638 i PGL M GGENATEB BECYCLIC THIOURETHANES Paul E. Hoch, Youngstown, N.Y., assignor to Hooker Chemiwl Corporation, N'agara Fails, N.Y., a corporation of New York No Drawing. Filed Aug. 28, 1962, Ser. No. 226,024

3 Claims. (Cl. 260-455) This invention relates to compositions of matter known as polyhalogen containing bicyclic diisocyanates, methods of preparing same, and derivatives thereof. More particularly the present invention resides in 3,4,5,6,7,7-hexahalo-3,6-endomethylene-1,2,3,6 tetrahydrobenzene --1,2- diisocyanate, the urethanes, thiourethanes and ureas thereof, wherein the halogen is selected from the group consisting of chlorine, bromine, fluorine, and mixture thereof.

The compositions of the present invention find utility in many applications. The diisocyanates of the present invention 'may be reacted with polymers containing hydroxyl or carboxyl groups We products which, dueto the high halogen content, are flame retardant in nature. In addition, the diisocyanates may mted with themselves or other diisocyanates, polyols, polyamines or polythiols togive highly useful polymeric products. The diisocyanates of the present invention find utility in a ricultural applications. and a.fla .-.P finga.

In addition, the diisocyanate derivativesfind utility in agriculturalapplications and in-the preparation of polymeric materials which, due to the high halogen content, are flame retardant in nature. reacted with formaldehyde to form fire-resistant urea-aldehyde-type resins. The urethanes and thiourethanes can he ester-interchanged with polyesters by heating in the presence of acid catalyst to cause incorporat of the bic\1g l i c l; a l0 enated nucle cule thereby rendering E e same fire-resistant. All of the ureas,'urethanes and thiourethanes can be incorporated as additives in polymeric compositions such' as'the polyurethanes togrender them fire resistant, a-.. t 1 Thecompounds'of the invention are"'represe nted by the following general iormulaz. r

Thus the ureas can be H o1-,, 00o1 H (5-01, zNaN, cri oooi I H 3,4,5,6,7,7-heraehlorosodium 3,6-methan01,2,3,6- azide tetrahydrophthaloyl chloride O 01 -OON3 A i 11 +2Na01 01- (L CONa diazide of hexachloro methano-tetrahydrophthaloyl chloride 01 H 01 Noo 1 1g 2N: Cl NCO 3,4,5,6,7,7'heraeh1oro-3,6-endornethylene- 1,2,3,Metrahydrobenzene-1,2-diisocyanate In the above reaction one mole of the heXachloro-methano-tetrahydro-phthaloyl'chloride is reacted with at least two moles of sodium azide. The starting material may also be fiuoro ,or bromo substituted. Alternatively mixed chloro, fiuoro, or bromo substituted compounds may be employed. Useful materials may also be obtained by substituting some of the halogens with aikoxy" groups. The following are examples of starting materials that can be used in the reaction: 3,4,5,6,7,7-hexabromo-3,6-methano-l,2,3,6- r tetrahydrophthalolylcliloride, 3,4,5,6-tetrachloro-7,7-difluoro-3,6-methano-- 1,2,3,6-tetrahydrophthaloyl chloride," 3,4,5,6-tetrachloro;7,7dibromo-3,6-methano- 1,2,3,6-tetrahydrophthaioyl chloride, 3,4,5,6,7-pentachloro-3,6*methano-1,2,3,6-

tetrahydrophthaloyl chloride, 3,4,5,6-tetrachloro-3,6-rnethano-l,2,3,6- tetrahydrophthaloyl chloride, and 3,4,5,6-tetrachloro-7,7-dimethoxy-3,6-methano 1,2,3,6-tetrahydrophthaloyl chloride.

The following are the corresponding products of the reaction: 3,4.'5,6,7,7-heXabromo-3,6-endomethylene-1,2,3,6-

tetrahydrobenzene-l,2-diisocyanate, 3,4,5,6-tetrachloro-7,7-ditluoro-3,6-endornethylene- 1,2,3,-tetrahydrobenzene-1,2-diisocyanate, 3,4,5,6-tetrachloro-7,7-dibromo-3,6-endornethylene- 1,2,3,6-tetrahydrobenzene-1,2-diisocyanate, 3,4,5,6,7-pentachloro-3,6-endomethylene-l,2,3,6-

tetrahydrobenzene-1,2-diisocyanate, 3,4,5,6-tetrachloro-3,6-endomethylene-1,2,3,6- tetrahydrobenzene-1,2-diisocyanate, and

unit 01 3 3,4,5,6-tetrachloro-7,7-d-imethoxy-3,6-endornethylene- 1,2,3,G-tetrahydrobenzene-1,2-diisocyanate.

Any alkali metal azide may be employed, for example, sodium, potassium, cesium, lithium, etc. The organic azide is preferably decomposed at temperatures in the range of about 60 to about 90 degrees centigrade.

The urethanes and thiourethanes of the present invention may be prepared from the diisocyanates of the present invention in accordance with the following equation given for the purpose of illustration.

E o1- l Noo ii .-O1:| RXH NCO.

LID-Cl; E Cl wherein R may be alkyl or aryl and wherein X may be .cene, as well as the corresponding mercapto compounds such as thiophenol, thiocresol, and the like. Generally,

- the aryl groups have six to twenty carbon atoms, preferably six to fourteen.

In addition, chloro-substituted alkyl and aryl compounds can be employed, such as 'Z-chloroethanol, 2-ch1oroethyl mercaptan, para-chlorophenol and para-chloro-thiophenol and the like. The reaction proceeds in the conventional manner by merely admixing the desired reactants. The reaction is slightly exothermic and requires cooling.

The ureas of the present invention may be prepared in accordance with the following equation given for the purposeof illustration.

H o1 noo -on Him). i ob 1,

wherein R is as defined heretofore. In addition a primary amine may be employed instead of a secondary amine, Le, a compound having the formula I CL: L.

4 Example 1 .-Preparat1'0n of 3,4,5,6,7,7 HexachI0r0-3,6- Endomeihylene 1,2,3,6 T etrahydrobenzene-J ,Z-Diisocyanate A suspension of 180 cubic centimeters dry chlorobenacne and 12.7 grams (0.196 mole) of sodium azide (activated previously with hydrazine and reprecipitated in acetone before use) was treated with 38 grams (0.089 mole) of 3,4,5,6,7,7 hexachloro 3,6 methanol-1,25,6- tetrahydrophthaloyl chloride. The suspension developed an exotherm and the temperature rose from 28 to 40 degrees centigrade in 15 minutes. Heat was then applied and the temperature was raised to 71 degrees centigrade at which point gas evolution was observed and a second exotherm took place. The temperature rose to 86 degrees centigrade and cooling Was resorted to. The suspension was maintained at a temperature of from about 64 to 77 degrees centigrade for 35 minutes, bringing the total reaction time to 2 hours and 40 minutes. The suspension was cooled to 25 degrees centigrade and filtered The filtrate was evaporated under vacuum on a steam cone. The residue, weighing thirty grams, was the expected product.

Analysis-Calculated fo'r C H Cl N O Cl, 55.6 percent. Found: 55.49 percent.

Example 2.-Preparati0n of a Polyurethane Foam Ten grams of an alkyd prepared by condensing 7.6 moles of glycerol, 5 moles of adipic acid and 1 mole of phthalic anhydride were rapidly mixed with 18 grams of the product of Example 1, and 0.4 cubic centimeter of a solution of 1.5 grams of N-methyl naphthalinc and 2.0 grams Emulphor in 96 grams water was added. The reaction mixture was stirred rapidly. Foaming began very rapidly. The mixture was poured into a paper cup and a rigid foam having a density of about 2 pounds per cubic foot formed within minutes. The foam was post cured at 100 degrees centigrade for one-half hour. The resulting foam was self extinguishing and did not melt when ignited.

Example 3.Preparati0n of the Dibutyl Urethane Derivarive, 3 ,4 ,5 6,7,7-H exach lore-3 ,6 -End0methylene-1 ,2,3 ,6- Telrahydrobenzene-I,Z-Bis-(Butyl Carbamate) A solution of 3.5 grams of the product of Example 1 and 25 milliliters of N-butyl alcohol was refluxed for 10 minutes. The solution resulting was cooled and a micro crystalline solid separated. This material was recrystallized twice from ethanol to yield 1 gram of the expected product which had a melting point of 163 to 163.5 degrees centigrade.

Analysis.Calculated for C H Cl O N Cl, 40.2 percent. Found: Cl, 40.1 percent.

Example 4 .Preparation of the Diethyl Urethane Deriva- .zive, 3,4,5,6,7,7-Hexachlore-3,6-Endomethylene-1,2,3,6-

T etrahydrobenzene-Z ,Z-Bis-(Ethyl Carbamate) A solution of 4 grams of the product of Example 1 and 25 cubic centimeters of ethanol were stirred. The reaction was mildy exothermic. After 10 minutes the excess alcohol was evaporated and the resulting solid was recrystallized several times from nitromethane to yield 1.5 grams of the expected product. The melting point was 215 to 216 degrees centigrade with sublimation.

AnaIysis.Calculated for C H Cl N O Cl, 44.8 percent. Found: Cl, 44.4 percent.

Example 5.-Preparalion of the Dfpropyl Urea Derivative 3,4,5,6,7,7-Hexach[om-3,o-Elzdomethylene-l,2,3,6- T elrahydrobenzene-J ,Z-Bis-(Isopropylurea) A solution of 7.6 grams of the product of Example 1 in 50 cubic centimeters of dry ether was treated with 5.05 grams of isopropyl amine in 50 cubic centimeters of ether. An exothermic reaction took place and a solid separated. The White solid weighing 4.6 grams was washed with ether. This material was recrystallized from benzene several times yielding the expected product which had a melting point of 191 to 192 degrees centigrade with decomposition.

Analysx's.Calculated for C H Cl O N Cl, 36.4 percent, N, 9.58 percent. Found: Cl, 36.6 percent, N, 9.3 percent.

Example 6.--Preparati0n of the Dibutyl T hiourethane Derivative, 3,4,5,6,7,7-Hexachloro-3,6-End0methylene-1,2, 3,6-Tetralzydrobenzene 1,2-Bis-(Butyl T hiocarbamate) A mixture of 10 grams of the product of Example 1 and 4.7 grams of n-butyl mercaptan was permitted to stand at 25 degrees centigrade overnight. The reaction mixture was warmed on a steam cone for 10 minutes, and then the solution cooled. The solid that formed was recrystallized four times from a cyclohexane-methanol solution to "'yield a solid which was the expected product and which 1. A compound having the formula:

wherein Y is selected from the group consisting of firmrine, chlorine, bromine and mixtures thereof; and R is selected from the group consisting of alkyl, aryl, chlorosubstituted alkyl, and chloro-substituted aryl, wherein alkyl has one to twelve carbon atoms and aryl has six to fourteen carbon atoms.

2. A compound having the formula:

wherein R is selected from the groups consisting of alkyl,

aryl chloro-substituted alkyl and chloro-substituted aryl; wherein alkyl has one to twelve carbon atoms and aryl has six to fourteen carbon atoms.

3. 3,4,5,6,7,7,-hexachloro 3,6-endomethylene-1,2,3,6- tetrahydrobenzene-1,2-bis-(butyl thiocarbamate) No references cited. 

1. A COMPOUND HAVING THE FORMULA: 